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SEDERHOLMITE, WILKMANITE, KULLERUDITE, M..AKINENITE and TRUSTEDTITE, FIVE NEW NICKEL SELENIDE MINERALS 1)

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SEDERHOLMITE, WILKMANITE, KULLERUDITE, M..AKINENITE and TRUSTEDTITE, FIVE NEW NICKEL SELENIDE MINERALS 1) T 4 SEDERHOLMITE, WILKMANITE, KULLERUDITE, M..AKINENITE and TRUSTEDTITE, FIVE NEW NICKEL SELENIDE MINERALS 1) BY Y. VUORELAINEN, A. HUHMA AND A. H.A.KLI Outokumpu Co., Finland ABSTRACT Five new nickel selenide minerals from Kuusamo, NE-Finland are described. The minerals occur in veinlets in albitites associated with uranium mineralisation. Sederholmite, which is identical with the synthetic hexagonal fJ-NiSe phase, has a o = 3.62 - 3.65 A and eo = 5.29 - 5.34 A depending upon composition. Wilkmanite corresponds to the artificial monoclinic Ni3Se4 phase. Its a o = 6.22 A, b o = 3.63 A, CO = 10.52 A and fJ = 90.55°. Kullerudite NiSe 2 is an ortho-rhombic nickelian analogue of ferroselite with a o = 4.89 A, b o = 5.96 A and Co = 3.76 A. M:ikinenite, which is the same as the artificial y-NiSe phase, has a trigonal symmetry with a o = 10.01 A and Co = 3.28 A. Triistedtite is a cubic spinel type Ni3Se4 having a o = 9.94 A. It forms a solid solution series with polydymite. Members of this series with 40-70 mole per cent polydymite component have also been found. CONTENTS Page INTRODUCTION 114 GEOLOGY OF THE SELENIUM MINERALISATION AREA 115 OCCURRENCE 116 PHYSICAL AND OPTICAL PROPERTIES 117 CHEMICAL COMPOSITION 117 CRYSTALLOGRAPHY 118 NOMENCLATURE 124 ACKNOWLEDGEMENTS 124 REFERENCES 125 1) Received May 6, 1964. 15 10547-64 114 Bulletin de la Commislsion geologique de Finlande N: 0 215. INTRODUCTION SI n The system nickel-selenium has been studied by various authors. Ac­ SI cording to the literature the following selenides of nickel are known. a-NiSe was obtained by Levi and Baroni (1935) by conducting ammonium selenide into a neutral nickel salt solution. The product was amorphous. ~-NiSe, which has a hexagonal structure of the NiAs type (Gr0nvold and Jacobsen, 1956, Hiller and Wegerner, 1960) has been prepared either by b heating appropriate amounts of the elements in evacuated and sealed silica o tubes (Gmnvold and Jacobsen, 1956) or by precipitating it with hydrogen SI selenide in a nickel acetate solution containing acetic acid (Levi and Baroni, a 1935). g y-NiSe has been obtained by Levi and Baroni (1935) by conducting a hydrogen selenide into a nickel sulphide solution containing sulphuric acid. Hiller and Wegener (1960) have also prepared y-NiSe by heating powdered G nickel and selenium at 225-250 Co. The compound is trigonal with a mill­ b erite type structure. NiSe 2 has been prepared by de Jong and Willems (1928) by heating a IS mixture of NiSe and selenium at 230 Co for 48 hours. It has also been synthe­ b tised by e.g. Gr0nvold and Jacobsen (1956), Hiller and Wegerner (1960) and Klemm (1962). The NiSe phase has a pyrite structure. 2 cl Ni3Se2 has been reported by Hiller and Wegener (1960). The phase is o hexagonal with a o = 6.029 A and Co = 7.249 A. T The Ni3Se 4 phase has also been prepared by Hiller and Wegenar (1960). s< A~cording to them it is monoclinic with a o = 12.15 A, b o = 3.633 A, Co = ~ 10.45 A and = 149°22'. Gr0nvold and Jacobsen (1956) have derived the Cl ~-NiSe structure of Ni3Se4 from that of the deformed hexagonal cell and b obtained different unit cell dimensions: a o = 6.196 A, b o = 3.634 A, Co = p ~ 10.464 A and = 90.78°. b Only two nickel selenide minerals have been reported so far. Blockite a (Ni,Cu)Se 2 was described by Herzenberg and Ahlfelt (1935) from Bolivia. tl In fact the mineral is the same as penroseite which was discovered in the h same locality and studied by Gordon (1925). Blockite is structurally similar to the artificial NiSe 2 • Robinson and Brooker (1952) reported a new nickel-bearing selenide, tyrrelite (Cu, Co, Ni)3Se4 from Beaverlodge Lake, Saskatchewan. They suggested that the mineral is structurally similar to pentlandite but Ma­ o chatschki (1952) has pointed out that the powder pattern oftyrrelite resem­ w bles_those of the spineI and linnaeite groups of minerals. A In conl).ections with the prospecting work carried out by the Outokumpu V Co in Kuusamo, in NE Finland during 1961-1963 quite a few new nickel w 1 Suomen Geologinen Seura. N: 0 36. Geologiska SaJlskapet i Finland. 115 selenide minerals were encountered. In this paper five of them i.e. p-NiSe, monoclinic Ni Se , y-NiSe, ortho-rhombic NiSe and cubic Ni Se are de­ Ac- a 4 2 a 4 scribed. illlum hous. GEOLOGY OF THE SELENIUM MINERALISATION AREA. i and In Kuusamo in NE Finland the Se-mineralisation occurs in albite dia­ er by bases which form sills in a schist formation. The schist formation is composed silica of quartzites, dolomites, marls, mica schists and black schists. Also green­ rogen schists are encountered. Quartzites are either clastic ortho-quartzites or lroni, albite-bearing arkose quarzites grading into dolomites. The marls are fine­ grained, predominantly grey, dolomite-bearing sediments which contain, cting apart from dolomite, quartz, micas and albite as major minerals. acid. Ripple marks, fossil mud cracks and clastic dikes are found in sediments. dered Graded bedding which permits the determination of the sedimentation mill- bottom is observed in mica schists and phyllites. In some localities phyllites contain carbon-bearing »bags» with calcite-rich cores. The size of the »bags» mg a is variable but the biggest attain a diametre of about 30 cm. They are nthe­ believed to be of fossil origin. ) and The green-schists, which may be, at least partly, of volcanic origin are chlorite-albite-epidote rocks often showing a distinct bedding. The bedding Lse IS of the schist formation dips subvertically. Folds as well as faults are common. The formation has locally tectonised intensively giving rise to transverse 960). schistosity. Co = Albite diabase is a hornblende-albite rock of variable grain size. Espe­ i the cially in strongly tectonised places it changes into more fine-grained biotite­ " and bearing rock which contains only a small amount of hornblende or is com­ Co = pletely free from it. Pink albitite is associated with these biotite-albite dia­ bases forming dikes or irregular bodies in the latter. Albitites occur prefer­ ckite ably at the ends or at the flexure points of the albite diabase sills, or near by livia. the country rock contacts i.e. generally in places where tectonisation has 1. the been strongest. milar Small amounts of sulphide, selenide and telluride minerals have been found in albitites, among them some hitherto unknown in geological litera­ nide, ture. These minerals are intimately associated with low-grade uranium min­ They eralisation and especially nickel selenides seem closely to follow uranium. Ma- Outside the uranium mineralisation the nickel content diminishes rapidly, :sem- whereas the amount of cobalt relative to that of nickel increases considerably. A similar correlation has been reported from Shinkolobwe by Derriks and lmpu Vaes (1955). In the wall rock cobalt is incorporated in the lattice of pyrite ickel which can contain up to 3 per cent cobalt. 116 Bulletin de la Commislsion geologique de Finlande N: 0 215. .1 ( The uranium mineralisation, which is confined to albitites, is not homo­ is co geneous but the uranium minerals occur as isolated spots and veinlets. The in th most important mineral is uranite, but brannerite, davidite, kasolite and 'I uranoanatase have also been identified as well as some alteration products afOrE of primary uranium minerals. crys1 II), I const toge1 OCCURRENCE NiTE have Among the new nickel selenides p-NiSe and monoclinic NiaSe4 form a natural and interesting pair. The artificial counterparts of these minerals idior have been prepared and reported by e.g. Levi and Baroni (1935), Gr0nvold and Jacobsen (1956) and Hiller and Wegener (1960). Since p-NiSe changes into monoclinic NiaSe4 by decreasing nickel content, both minerals occur associated most intimately with each other. They are found almost exclu­ '1 sively in blockite clusters of a few millimetres in diametre, which seem to sitio: favour calcite veinlets in the uranium-bearing parts of albitite dikes. fJ-NiSe is di and monoclinic Ni Se brecciate blockite forming micro-veinlets and flame­ 3 4 greeJ like segregations in it as is seen in Fig. 1, Plate 1. p-NiSe has also been detected yellc as independent grains in clausthalite. Monoclinic NiaSe4 seems to occur either clini, as a primary or secondary mineral. The latter is an alteration product of yellc P-NiSe. The secondary monoclinic NiaSe4 often gives a diffuse powder pattern Botl with the consequence that only the strongest reflections are visible. Mono­ '1 clinic Ni Se is frequently followed by native secondary selenium and some­ a 4 exce times -also by ferroselite. Selenian vaesite and selenian cattierite also belong and to the mineral paragenesis but they are younger than blockite, fJ-NiSe and minE monoclinic NiaSe4 , for they form veinlets cutting the latter. (Sec Fig. 1, I Plate I). is stJ The ortho-rhombic NiSe seems to occur almost exclusively as an altera­ 2 pale tion product of monoclinic NiaSe4 • The mineral grains often contain relics cind of the latter as indicated by Fig. 2, PlateI, but in some cases the primary ( mineral has completely disappeared. The formation of the ortho- rhombic is hi NiSe has taken place soon after the crystallisation of fJ-NiSe and monoclinic 2 hloc: Ni Se but before the appearance of selenian sulphides, for they are seen to 3 4 take cut ortho-rhombic NiSe • In spite of the fact that ortho-rhombic NiSe is a 2 2 NiaS nickelian analogue of ferroselite it has never been observed in association with the latter.
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